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1.
Single crystals of Li-aegirine LiFe3+Si2O6 were synthesized at 1573?K and 3?GPa, and a polycrystalline sample suitable for neutron diffraction was produced by ceramic sintering at 1223?K. LiFe3+Si2O6 is monoclinic, space group C2/c, a=9.6641(2)?Å, b= 8.6612(3)?Å, c=5.2924(2)?Å, β=110.12(1)° at 300?K as refined from powder neutron data. At 229?K Li-aegirine undergoes a phase transition from C2/c to P21 /c. This is indicated by strong discontinuities in the temperature variation of the lattice parameters, especially for the monoclinic angle β and by the appearance of Bragg reflections (hkl) with h+k≠2n. In the low-temperature form two non-equivalent Si-sites with 〈SiA–O〉=1.622?Å and 〈SiB–O〉=1.624?Å at 100?K are present. The bridging angles of the SiO4 tetrahedra O3–O3–O3 are 192.55(8)° and 160.02(9)° at 100?K in the two independent tetrahedral chains in space group P21 /c, whereas it is 180.83(9)° at 300?K in the high-temperature C2/c phase, i.e. the chains are nearly fully expanded. Upon the phase transition the Li-coordination changes from six to five. At 100?K four Li–O bond lengths lie within 2.072(4)–2.172(3)?Å, the fifth Li–O bond length is 2.356(4)?Å, whereas the Li–O3?A bond lengths amount to 2.796(4)?Å. From 57Fe Mössbauer spectroscopic measurements between 80 and 500?K the structural phase transition is characterized by a small discontinuity of the quadrupole splitting. Temperature-dependent neutron powder diffraction experiments show first occurrence of magnetic reflections at 16.5?K in good agreement with the point of inflection in the temperature-dependent magnetization of LiFe3+Si2O6. Distinct preordering phenomena can be observed up to 35?K. At the magnetic phase transition the unit cell parameters exhibit a pronounced magneto-striction of the lattice. Below T N Li-aegirine shows a collinear antiferromagnetic structure. From our neutron powder diffraction experiments we extract a collinear antiferromagnetic spin arrangement within the a–c plane.  相似文献   

2.
Single crystals of C–Na2Si2O5 have been synthesized from the hydrothermal recrystallization of a glass. The title compound is monoclinic, space group P21/c with Z= 8 and unit-cell parameters a= 4.8521 (4)Å, b=23.9793(16)Å, c=8.1410(6)Å, β=90.15(1)° and V=947.2(2)Å3. The structure has been determined by direct methods and belongs to the group of phyllosilicates. It is based on layers of tetrahedra with elliptically six-membered rings in chair conformation. The sequence of directedness within a single ring is UDUDUD. The sheets are parallel to (010) with linking sodium cations in five- and sixfold coordination. Concerning the shape and the conformation of the rings, C–Na2Si2O5 is closely related to β-Na2Si2O5. However, both structures differ in the stacking sequences of the layers. A possible explanation for the frequently observed polysynthetic twinning of phase C is presented. In the 29Si MAS-NMR spectrum of C–Na2Si2O5 four well-resolved lines of equal intensity are observed at ?86.0, ?86.3, ?87.4, and ?88.2?ppm. The narrow range of isotropic chemical shifts reflects the great similarity of the environments of the different Si sites. This lack of pronounced differences in geometry renders a reliable assignment of the resonance lines to the individual sites on the basis of known empiric correlations and geometrical features impossible.  相似文献   

3.
A new superstructure was found in bafertisite [(Ba0.98Na0.02)1.00(Fe1.71Mn0.26Mg0.01)1.98 TiO[(Si1.82Ti0.04Al0.03Cr0.01)1.90O7](OH1.40F0.53Cl0.03)1.96] from Donghai County, Jiangsu Province, China. The occurrence of the superstructure reflections were observed by single crystal diffraction using a SMAR APEX CCD. The a*, b*and c* axis directions revealed extra weak reflection spots of the superstructure. The apparent 2a, 2b and 2c superstructure is monoclinic with unit cell a＝10.6502(15)?, b＝13.7233(19)?, c＝21.6897(3)?, α＝90o, β＝94.698(3)o, γ＝90o,space group Cm,Z=16. If c* extra weak reflections are ignored, the secondary supercell gave a cell a＝10.6548(15)?, b＝13.7284(19)?, c＝11.6900(17)?, α＝90o, β＝112.322(28)o, γ＝90o,space group Cm,Z=8. The basic subcell was obtained by ignoring all extra weak reflection spots and gave: a＝5.3249(17)?, b＝6.8669(22)?, c＝10.8709(36)?, α＝90o, β＝94.740(62)o, γ＝90o,space P21/m,Z=2. The superstructure has been refined to R = 0.063 for 7805 [R(int) = 0.0266] unique reflections I>2δ(I). The structure consists of an octahedra (O) sheet sandwiched between two heteropolyhedral (H) sheets. These sheets consist of Ti–octahedra and twin tetrahedral disilicate groups [Si2O7]. The O sheet comprises (Fe,Mg)O4 octahedra. The large Ba cation is located in the interlayer area. The refined structure shows Fe, Mg are partly ordered. The shifting of the TiO6 octahedron and SiO4 tetrahedron sites in the sheet may be a consequence of the superstructure.  相似文献   

4.
Using single-crystal X-ray diffraction from a diamond anvil cell, the compressibility of a synthetic fluorapatite was determined up to about 7?GPa. The compression pattern was anisotropic, with greater change along a than c. Unit cell parameters varied linearly with β a =3.32(8)?10?3 and β c =2.40(5)?10?3 GPa?1, giving a ratio β a :β c =1.38:1. Data fitted with a third-order Birch-Murnaghan EOS yielded a bulk modulus of K 0=93(4)?GPa with K′=5.8(1.8). The evolution of the crystal structure of fluorapatite was analysed using data collected at room pressure, at 3.04 and 4.72?GPa. The bulk modulus of phosphate tetrahedron is about three times greater than the bulk modulus of calcium polyhedra. The values were 270(10), 100(4) and 86(3) GPa for P, Ca1 (nine-coordinated) and Ca2 (seven-coordinated) respectively. While the calcium polyhedra became more regular with pressure, the distortion of the phosphate tetrahedron remained unchanged. The size of the channel extending along the [001] direction represented the most compressible direction. The Ca2–Ca2 distance decreased from 3.982 to 3.897?Å on compression from 0.0001 to 4.72?GPa. The anisotropic compressional pattern may be understood in terms of the greater compressibility of the channel size over the polyhedral units. The reduction of the channel volume was measured by the evolution of the trigonal prism, having the Ca2–Ca2–Ca2 triangle as its base and the c lattice parameter as its height. This prism volume changed from 47.3?Å3 at room pressure to 44.78?Å3 at 4.72?GPa. Its relatively high bulk moduli, 86(3) GPa, indicated that the channel did not collapse with pressure and the apatite structure could remain stable at very high pressure.  相似文献   

5.
A natural Ca-rich pigeonite (En47Fs43Wo10), free of augite exsolution products, was studied by in situ high-temperature single-crystal X-ray diffraction. The sample, monoclinic P2 1 /c (a=9.719(7) Å, b=8.947(9) Å, c=5.251(3) Å, β=108.49(5), V=433.0(6) Å3), was annealed up to 1000 °C to induce a phase transition from P2 1 /c to C2/c symmetry. Complete single-crystal X-ray diffraction data collections were carried out in situ at 650, 750, 850 and 950 °C after the crystal had reached equilibrium for the Fe–Mg intracrystalline exchange reaction at each temperature. The variation, with increasing temperature, of lattice parameters, of intensity of hkl reflections with h + k=2n + 1 (which vanish at high temperature) and of some geometrical parameters from structure refinement, showed that the displacive phase transition P2 1 /c?C2/c was continuous in character. This contrasts with the first-order character for the HT phase transition in pigeonite containing significantly less calcium.  相似文献   

6.
The nickel arsenide (B81) and related crystal structures are among the most important crystallographic arrangements assumed by Fe and Ni compounds with light elements such as Si, O, S, and P, expected to be present in planetary cores. Despite the simple structure, some of these materials like troilite (FeS) exhibit complex phase diagrams and rich polymorphism, involving significant changes in interatomic bonding and physical properties. NiP (oP16) represents one of the two principal structure distortions found in the nickel arsenide family and is characterized by P–P bonding interactions that lead to the formation of P2 dimers. In the current study, the single-crystal synchrotron X-ray diffraction technique, aided by first principles density functional theory (DFT) calculations, has been applied to examine the compression behavior of NiP up to 30 GPa. Two new reversible displacive phase transitions leading to orthorhombic high-pressure phases with Pearson symbols oP40 and oC24 were found to occur at approximately 8.5 and 25.0 GPa, respectively. The oP40 phase has the primitive Pnma space group with unit cell a = 4.7729(5) Å, b = 16.6619(12) Å, and c = 5.8071(8) Å at 16.3(1) GPa and is a superstructure of the ambient oP16 phase with multiplicity of 2.5. The oC24 phase has the acentric Cmc21 space group with unit cell a = 9.695(6) Å, b = 5.7101(9) Å, and c = 4.7438(6) Å at 28.5(1) GPa and is a superstructure of the oP16 phase with multiplicity of 1.5. DFT calculations fully support the observed sequence of phase transitions. The two new phases constitute logical next stages of P sublattice polymerization, in which the dilution of the P3 units, introduced in the first high-pressure phase, decreases, leading to compositions of Ni20(P3)4(P2)4 and Ni12(P3)4, and provide important clues to understanding of phase relations and transformation pathways in the NiAs family.  相似文献   

7.
Two samples of hydroxyl-clinohumite, sample SZ0407B with approximate composition Mg8.674(14)Fe0.374(4)(Si0.99(1)O4)4(OH)2 and sample SZ0411B with composition Mg9(SiO4)4(OH)2, were synthesized at 12 GPa and 1,250 °C coexisting with olivine. Unit-cell parameters determined by single-crystal X-ray diffraction are given as follows: a = 4.7525(4) Å, b = 10.2935(12) Å, c = 13.7077(10) Å, α = 100.645(9)°, V = 659.04(9) Å3 for SZ0407B, and a = 4.7518(6) Å, b = 10.2861(12) Å, c = 13.7008(9) Å, α = 100.638(9)°, V = 658.15(9) Å3 for SZ0411B. Single-crystal X-ray intensity data were collected for crystal structure refinements of both samples. Relative to the pure-Mg sample, Fe decreases M3–OH bond lengths by ~0.010(3) Å, consistent with some ferric iron ordering into M3. Raman spectroscopy shows two strong bands in the lattice-mode region at 650 and 690 cm?1 in the Fe-bearing sample, which are not observed in the pure-Mg sample. Spectra in the H2O region show at least five bands, which are deconvolved into seven distinct O–H-stretching modes. Thermal expansion measurements were carried out for both samples from 153 to 787 K by single-crystal X-ray diffraction. The average a-, b-, c-axial and volumetric thermal expansion coefficients (10?6 K?1) are 10.5(1), 12.3(2), 12.5(2) and 34.9(5) for SZ0407B, respectively, and 11.1(1), 12.6(3), 13.7(3), 36.8(6) for SZ0411B, respectively. After heating, the unit-cell parameters were refined again for each sample at ambient condition, and no significant changes were observed, indicating no significant oxidation or dehydration during the experiment. For the DHMS phases along the brucite–forsterite join, linear regression gives a systematic linear decrease in expansivity with increasing density. Further, substitution of ferrous iron into these structures decreases thermal expansivity, making the Fe-bearing varieties slightly stiffer.  相似文献   

8.
A series of fluoride perovskites related to neighborite was investigated using X-ray and neutron diffraction techniques, and Rietveld profile refinement of powder diffraction data. The series (Na1? x K x )MgF3 comprises orthorhombic (Pbnm, a?≈? , b?≈? , c?≈?2a p , Z=4) perovskites in the compositional range 0?≤?x?≤?0.30, tetragonal perovkites (P4/mbm, a?≈? , c?≈?a p , Z=2) in the range 0.40?≤?x?≤?0.46, and cubic phases (Pm3¯m, Z=1) for x?>?0.50. The structure of the orthorhombic neighborite is derived from the perovskite aristotype by rotation of MgF6 octahedra about the [110] and [001] axes of the cubic subcell. The degree of rotation, measured as a composite tilt Φ about the triad axis, varies from 18.2° at x=0 to 11.2° at x=0.30 (as determined from the fractional atomic coordinates). Orthorhombic neighborite also shows a significant displacement of Na and K from the “ideal” position (≤0.25?Å). The tetragonal members of the neighborite series exhibit only in-phase tilting about the [001] axis of the cubic subcell (φ) ranging from 4.5° to 4.8° (determined from the atomic coordinates). The solid solution (Na1? x K x )MgF3, shows a regular variation of unit-cell dimensions with composition from 3.8347?Å for the end-member NaMgF3 (reduced to pseudocubic subcell, a p ) to 3.9897?Å for KMgF3. This variation is accompanied by increasing volumes of the A-site polyhedra, whereas the volume of MgF6 octahedra initially decreases (up to x=0.40), and then increases concomitantly with K content. The polyhedral volume ratio, V A /V B , gradually increases towards the tetragonal structural range, in agreement with diminishing octahedral rotation in the structure. The P4/mbm-type neighborite has an “anomalous” polyhedral volume ratio (ca. 5.04) owing to the critical compression of MgF6 polyhedra.  相似文献   

9.
The space group of an orthopyroxene (En86) from a deep crustal lunar rock (sample 76535) that was previously reported as having space group P21 ca has been re-examined on an automated X-ray diffractometer. In addition to diffractions violating the b-glide of the conventional space group, Pbca (0kl,k-odd) reported in the earlier study, diffractions violating the a-glide of Pbca are also present. Careful examination of both the a-glide- and b-glide-violations shows them to be sharp, with no evidence of diffuse streaks parallel to a *, and with consistent intensities at several rotations about ψ. Diffractions violating the b-glide are in registry with the host, however, those violating the a-glide appear to be out of registry and result from a cell with a slightly longer a of about 18.4 Å, consistent with previous electron diffraction studies. The most reasonable explanation for the observed space group violations is that both the a- and b-glide violations result from ordering of Ca into (100) Guinier-Preston (G-P) zones that possess orthopyroxene topology, but have space group P21/c and a cell of a=18.4 Å, b=8.83 Å, c=5.18 Å, and β=90.0°; whereas the Cadepleted host has space group Pbca and a cell of a= 18.230(6) Å, b = 8.828(2) Å, and c=5.1946(9) Å. In addition to the G-P zones which may compose 12% or more of the sample, the crystal contains (100) lamellae of pigeonite, and other samples from the same rock contain lamellae of augite.  相似文献   

10.
Single crystal synthesis, X-ray powder diffraction data, and electron microprobe data are given for some Na rare earth silicates of the types NaMSiO4, Na3MSi2O7, Na3MSi3O9, and Na5MSi4O12. NaYSiO4 is orthorhombic with SG Pbn21, a=5.132, b=11.156, anc c=6.405 Å. NaGdSiO4 is tetragonal with SG I4 or I \(\bar 4\) with a=11.743 and c=5.444 Å. A second form of NaGdSiO4 is orthorhombic with SG P21 nb or Pmmb, a=9.179, b=27.29, and c=5.472 Å. Na3YSi2O7 is hexagonal with a=9.416 and c=13.776 Å. Na3YSi3O9 is orthorhombic with a=15.215, b=15.126, and c=15.036 Å. Na ion conductivities of Na3YSi2O7 and Na3YSi3O9 at 300° C of 5×10?6 (Θ-cm)?1 and 6×10?6 (Θ-cm)?1, respectively, are substantially less than that for Na6YSi4O12, 1×10?1 (Θ-cm)?1.  相似文献   

11.
Polycrystalline material of a sulfate apatite with chemical composition Na6Ca4(SO4)6F2 or (Na2Ca4)Na4(SO4)6F2 has been synthesized by solid state reactions. Basic crystallographic data are as follows: hexagonal symmetry, a?=?9.3976(1) Å, c?=?6.8956(1) Å, V?=?527.39(1) Å3, Z?=?1, space group P63/m. For structural investigations the Rietveld method was employed. Thermal expansion has been studied between 25 and 600 °C. High temperature (HT) powder diffraction data as well as thermal analysis indicate that the apatite-type compound undergoes a reconstructive phase transition in the range between 610 and 630 °C. Single-crystals of the HT-polymorph were directly grown from the melt. Structural investigations based on single-crystal diffraction data of the quenched crystals performed at ?100 °C showed orthorhombic symmetry (space group Pna21) with a?=?12.7560(8) Å, b?=?8.6930(4) Å, c?=?9.8980(5) Å, V?=?1097.57(10) Å3 and Z?=?2. Unit cell parameters for a quenched polycrystalline sample of the HT-form obtained at ambient conditions from a LeBail-fit are as follows: a?=?12.7875(1) Å, b?=?8.7255(1) Å, c?=?9.9261(1) Å, V?=?1107.53(2) Å3. The lattice parameters of both modifications are related by the following approximate relationships: a HT?≈?2c RT, b HT?≈?-(½a RT?+?b RT), c HT?≈?a RT. The HT-modification is isotypic with the corresponding potassium compound K6Ca4(SO4)6F2. The pronounced disorder of the sulphate group even at low temperatures has been studied by maximum entropy calculations. Despite the first-order character of the transformation clusters of sulfate groups surrounding the fluorine anions can be identified in both polymorphs. Each of the three next neighbor SO4-tetrahedra within a cluster is in turn surrounded by 8–9 M-cations (M: Na,Ca) defining cage-like units. However, in the apatite structure the corresponding three tricapped trigonal prisms are symmetry equivalent. Furthermore, the central fluorine atom of each cluster is coordinated by three next M-neighbors (FM3-triangles), whereas in the HT-polymorph a four-fold coordination is observed (FM4-tetrahedra).  相似文献   

12.
The existence of an incomplete solid solution series between loparite (NaLREETi2O6), a member of the perovskite mineral group, and thorutite (ThTi2O6) is established on the basis of experimental and mineralogical data. The products of low- and high-pressure synthesis in the system NaLaTi2O6– ThTi2O6 were studied by energy-dispersive spectrometry, X-ray diffractometry and Rietveld analysis. At atmospheric pressure, Th is incorporated in loparite as both ThTi2O6 and Na2ThTi3O9. In synthetic systems, the maximum determined ThTi2O6 content of loparite is 18 mol%, with a corresponding A-site cation deficiency of 9%. The structure of such loparite is tetragonal and presumably derived from the cubic aristotype by octahedral rotation [I4/mcm, a=5.4652(1) Å, c=7.7476(2) Å]. At a pressure of 6 GPa, no solubility between loparite and ThTi2O6 is observed, and Th is accommodated in the loparite structure entirely as Na2ThTi3O9 (up to 30 mol%). Naturally occurring loparite contains up to 29 mol% ThTi2O6, based on the conventional method of analysis recalculation, or 23.5 mol% ThTi2O6, assuming the presence of protons at the vacant A-sites. ThTi2O6 synthesized by the solid-state reaction, crystallizes with monoclinic symmetry [C2/m, a=9.8140(2) Å, b=3.8228(1) Å, c=7.0313(2) Å,β=118.82(1)°]. Atomic coordinates for ThTi2O6 obtained in this study from X-ray powder data, as well as structural parameters derived from the new data, are in a good agreement with those known from single-crystal refinement. ThTi2O6 does not crystallize at high pressure, and Th is accommodated in perovskite-type compounds and cubic ThO2 that provide a twelve- and eight-fold coordination site for Th, respectively.  相似文献   

13.
The single-crystal of humboldtine [Fe2+(C2O4) · 2H2O] was first synthesized and the crystal structure has been refined. Single-crystal X-ray diffraction data were collected using an imaging-plate diffractometer system and graphite-monochromatized MoKα radiation. The crystal structure of humboldtine was refined to an agreement index (R1) of 3.22% calculated for 595 unique observed reflections. The mineral crystallizes in the monoclinic system, space group C2/c, with unit cell dimensions of a = 12.011 (11), b = 5.557 (5), c = 9.920 (9) Å, β = 128.53 (3)?, V = 518.0 (8) Å3, and Z = 4. In this crystal structure, the alternation of oxalate anions [(C2O4)2?] and Fe2+ ions forms one-dimensional chain structure parallel to [010]; water molecules (H2O)0 create hydrogen bonds to link the chains, where (H2O)0 is essentially part of the crystal structure. The water molecules with the two lone electron pairs (LEPs) on their oxygen atom are tied obliquely to the chains, because the one lone electron pair is considered to participate in the chemical bonds with Fe2+ ions. Humboldtine including hydrogen bonds is isotypic with lindbergite [Mn2+(C2O4) · 2H2O]. The donor–acceptor separations of the hydrogen bonds in humboldtine are slightly shorter than those in lindbergite, which suggests that the hydrogen bonds in the former are stronger than those in the latter. The infrared and Raman spectra of single-crystals of humboldtine and lindbergite confirmed the differences in hydrogen-bond geometry. In addition, Fe2+–O stretching band of humboldtine was split and broadened in the observed Raman spectrum, owing to the Jahn–Teller effect of Fe2+ ion. These interpretations were also discussed in terms of bond-valence theory.  相似文献   

14.
MgSiO3 akimotoite is stable relative to majorite-garnet under low-temperature geotherms within steeply or rapidly subducting slabs. Two compositions of Mg–akimotoite were synthesized under similar conditions: Z674 (containing about 550 ppm wt H2O) was synthesized at 22 GPa and 1,500 °C and SH1101 (nominally anhydrous) was synthesized at 22 GPa and 1,250 °C. Crystal structures of both samples differ significantly from previous studies to give slightly smaller Si sites and larger Mg sites. The bulk thermal expansion coefficients of Z674 are (153–839 K) of a 1 = 20(3) × 10?9 K?2 and a 0 = 17(2) × 10?6 K?1, with an average of α 0 = 27.1(6) × 10?6 K?1. Compressibility at ambient temperature of Z674 was measured up to 34.6 GPa at Sector 13 (GSECARS) at Advanced Photon Source Argonne National Laboratory. The second-order Birch–Murnaghan equation of state (BM2 EoS) fitting yields: V 0 = 263.7(2) Å3, K T0 = 217(3) GPa (K′ fixed at 4). The anisotropies of axial thermal expansivities and compressibilities are similar: α a  = 8.2(3) and α c  = 10.68(9) (10?6 K?1); β a  = 11.4(3) and β c  = 15.9(3) (10?4 GPa). Hydration increases both the bulk thermal expansivity and compressibility, but decreases the anisotropy of structural expansion and compression. Complementary Raman and Fourier transform infrared (FTIR) spectroscopy shows multiple structural hydration sites. Low-temperature and high-pressure FTIR spectroscopy (15–300 K and 0–28 GPa) confirms that the multiple sites are structurally unique, with zero-pressure intrinsic anharmonic mode parameters between ?1.02 × 10?5 and +1.7 × 10?5 K?1, indicating both weak hydrogen bonds (O–H···O) and strong OH bonding due to long O···O distances.  相似文献   

15.
In order to confirm the possible existence of FeGeO3 perovskite, we have performed in situ X-ray diffraction measurements of FeGeO3 clinopyroxene at pressures up to 40 GPa at room temperature. The transition of FeGeO3 clinopyroxene into orthorhombic perovskite is observed at about 33GPa. The cell parameters of FeGeO3 perovskite are a=4.93(2) Å, b=5.06(6) Å, c=6.66(3) Å and V=166(3) Å3 at 40 GPa. On release of pressure, the perovskite phase transformed into lithium niobate structure. The previously reported decomposition process of clino-pyroxene into Fe2GeO4 (spinel)+GeO2 (rutile) or FeO (wüstite) +GeO2 (rutile) was not observed. This shows that the transition of pyroxene to perovskite is kinetically accessible compared to the decomposition processes under low-temperature pressurization.  相似文献   

16.
Synthetic, flux-grown uvarovite, Ca3Cr2 [SiO4]3, was investigated by optical methods, electron microprobe analysis, UV-VIS-IR microspectrometry, and luminescence spectroscopy. The crystal structure was refined using single-crystal X-ray CCD diffraction data. Synthetic uvarovite is optically isotropic and crystallizes in the “usual” cubic garnet space group Ia3¯d [a=11.9973 Å, Z=8; 21524 reflections, R1=2.31% for 454 unique data and 18 variables; Cr–O=1.9942(6), Si–O=1.6447(6), Ca–Oa=2.3504(6), Ca–Ob= 2.4971(6) Å]. The structure of Ca3Cr2[SiO4]3 complies with crystal-chemical expectations for ugrandite group garnets in general as well as with predictions drawn from “cubically averaged” data of non-cubic uvarovite–grossular solid solutions (Wildner and Andrut 2001). The electronic absorption spectra of Cr3+ in trigonally distorted octahedra of synthetic uvarovite were analyzed in terms of the superposition model (SM) of crystal fields. The resulting SM and interelectronic repulsion parameters are =9532 cm?1, =4650 cm?1, power law exponent t 4=6.7, Racah B35=703 cm?1 at 290 K (reference distance R 0=1.995 Å; fixed power law exponent t 2=3 and spin-orbit parameter ζ=135 cm?1). The interelectronic repulsion parameters Racah B 55=714 cm?1 and C=3165 cm?1 were extracted from spin-forbidden transitions. This set of SM parameters was subsequently applied to previously well-characterized natural uvarovite–grossular solid solutions (Andrut and Wildner 2001a; Wildner and Andrut 2001) using their extrapolated Cr–O bond lengths to calculate the energies of the spin-allowed bands. These results are in very good agreement with the experimentally determined band positions and indicate the applicability of the superposition model to natural 3d N prevailing systems in geosciences. Single-crystal IR absorption spectra of synthetic uvarovite in the region of the OH-stretching vibration exhibit one isotropic absorption band at 3508 cm?1 at ambient conditions, which shifts to 3510 cm?1 at 77 K. This band is caused by structurally incorporated hydroxyl groups via the (O4H4)-hydrogarnet substitution. The water content, calculated using an integral extinction coefficient ?=60417 cm?2 l mol?1, is c H2O=33 ppm.  相似文献   

17.
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18.
We have collected high-resolution neutron powder diffraction patterns from MgSO4·11D2O over the temperature range 4.2–250 K. The crystal is triclinic, space-group \( \text{P} \bar{1} \) (Z = 2) with a = 6.72746(6) Å, b = 6.78141(6) Å, c = 17.31803(13) Å, α = 88.2062(6)°, β = 89.4473(8)°, γ = 62.6075(5)°, and V = 701.140(6) Å3 at 4.2 K, and a = 6.75081(3) Å, b = 6.81463(3) Å, c = 17.29241(6) Å, α = 88.1183(3)°, β = 89.4808(3)°, γ = 62.6891(3)°, and V = 706.450(3) Å3 at 250 K. Structures were refined to wRp = 3.99 and 2.84% at 4.2 and 250 K, respectively. The temperature dependence of the lattice parameters over the intervening range have been fitted with a modified Einstein oscillator model which was used to obtain the coefficients of the thermal expansion tensor. The volume thermal expansion, αV, is considerably smaller than ice Ih at all temperatures, and smaller even than MgSO4·7D2O (although ?αV/?T is very similar for both sulfates); MgSO4·11D2O exhibits negative αV below 55 K (compared to 70 K in D2O ice Ih and 20 K in MgSO4·7D2O) The relationship between the magnitude and orientation of the principal axes of the expansion tensor and the main structural elements are discussed.  相似文献   

19.
High-pressure phase transitions of CaRhO3 perovskite were examined at pressures of 6–27 GPa and temperatures of 1,000–1,930°C, using a multi-anvil apparatus. The results indicate that CaRhO3 perovskite successively transforms to two new high-pressure phases with increasing pressure. Rietveld analysis of powder X-ray diffraction data indicated that, in the two new phases, the phase stable at higher pressure possesses the CaIrO3-type post-perovskite structure (space group Cmcm) with lattice parameters: a = 3.1013(1) Å, b = 9.8555(2) Å, c = 7.2643(1) Å, V m  = 33.43(1) cm3/mol. The Rietveld analysis also indicated that CaRhO3 perovskite has the GdFeO3-type structure (space group Pnma) with lattice parameters: a = 5.5631(1) Å, b = 7.6308(1) Å, c = 5.3267(1) Å, V m  = 34.04(1) cm3/mol. The third phase stable in the intermediate P, T conditions between perovskite and post-perovskite has monoclinic symmetry with the cell parameters: a = 12.490(3) Å, b = 3.1233(3) Å, c = 8.8630(7) Å, β = 103.96(1)°, V m  = 33.66(1) cm3/mol (Z = 6). Molar volume changes from perovskite to the intermediate phase and from the intermediate phase to post-perovskite are –1.1 and –0.7%, respectively. The equilibrium phase relations determined indicate that the boundary slopes are large positive values: 29 ± 2 MPa/K for the perovskite—intermediate phase transition and 62 ± 6 MPa/K for the intermediate phase—post-perovskite transition. The structural features of the CaRhO3 intermediate phase suggest that the phase has edge-sharing RhO6 octahedra and may have an intermediate structure between perovskite and post-perovskite.  相似文献   

20.
Tremolite–tschermakite solid solutions have been synthesized between 700 and 850 °C and 200 and 2000 MPa. The starting materials were oxide–hydroxide mixtures and an additional 0.1–1.8 molal CaBr2 solution. The run products were characterized using SEM, HRTEM, EMP, XRD and FTIR. The synthesized Al tremolites formed needles and lath-shaped crystals of up to 300 × 20 μm. HRTEM investigations showed that the majority of the amphiboles were well ordered. The EMP analysis revealed that the Al tremolites were solid solutions in the ternary tremolite–tschermakite–cummingtonite. The highest observed Al content was close to the composition of magnesiohornblende (Xts=0.54). Different cummingtonite concentrations (Xcum=0.00–0.18) were observed, which generally increased with Al content. Rietveld refinements of the lattice constants showed a linear decrease of the cell parameters a and b with increasing Al content, whereas c and β increased. Small deviations from the linear behaviour were caused by variable amounts of the cummingtonite component. For pure tschermakite lattice parameters of a=9.7438(11) Å, b=17.936(14) Å, c=5.2995(3) Å, β=105.68(9)° and V=891.7 ± 1.4 Å3 were extrapolated by least-squares regression. Using the a and β lattice parameters for tremolite, tschermakite and cummingtonite, it was possible to derive amphibole compositions using powder XRD. IR spectra of the Al tremolites showed a total of 12 individual bands. The FWHMs of all bands increased with increasing Al content. According to their FWHMs, these bands were grouped into three band systems at 3664–3676 cm?1 (I), 3633–3664 cm?1 (II) and 3526–3633 cm?1 (III). Assuming [6]Al substitution at M2 and/or M3 and [4]Al at T1, three principal different configurational groups could be assigned as local environments for the proton. I: only Si4+ at T1 and one or two Al3+ at M2 and/or M3far, II: one Al3+ at T1 and one to three Al3+ at M2 and/or at M3far, III: either Al3+ on M3near and/or two Al3+ on T1 and additional one to four Al3+ at M2. It is assumed that these three configurational groups correspond to the three groups of observed bands. This was quantitativly supported by Monte-Carlo simulations. A model with random distribution at M2 and M3 including Al avoidance at tetrahedral and octahedral sites yielded the best agreement with the spectroscopical results.  相似文献   

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